Reliable assessment of the potential alkali reactivity of aggregate to develop deleterious alkali-silica reaction is essential for construction of durable concrete structures. The potential alkali reactivity of silicified limestone and two limestones has been investigated. Preliminary characterisation of aggregate was performed by optical and environmental scanning electron microscopy. X-ray powder diffraction peak profile analysis was used to predict the aggregates' potential alkali reactivity. Samples were aged in accordance to the RILEM AAR-2 procedure and further characterised by means of optical and environmental scanning electron microscopy as well as by synchrotron X-ray microtomography, where quantitative analysis relative to damage due to the alkali-silica reaction (ASR) was performed by morphometric analysis of volume data. Results highlight that (1) the microstructural domain size and microstrain values extracted form XRPD line profile analysis seem to be good parameters for predicting the potential alkali reactivity of quartz in aggregate, and (2) the mineralogy of the aggregate influences the weathering products (i.e. aggregate dissolution, ASR gel growth and microcracking) due to ASR in cement-based materials.